U.S. patent application number 14/390703 was filed with the patent office on 2015-03-19 for polycondensation product based on aromatic compounds, method for the preparation and use thereof.
The applicant listed for this patent is Construction Research & Technology, GmbH. Invention is credited to Frank Dierschke, Torben Gadt, Uwe Gehrig, Klaus Hartl, Michael Melchart, Tatiana Mitkina, Maxim Pulkin, Peter Schwesig, Madalina Andreea Stefan, Mario Vierle.
Application Number | 20150080500 14/390703 |
Document ID | / |
Family ID | 48446247 |
Filed Date | 2015-03-19 |
United States Patent
Application |
20150080500 |
Kind Code |
A1 |
Dierschke; Frank ; et
al. |
March 19, 2015 |
POLYCONDENSATION PRODUCT BASED ON AROMATIC COMPOUNDS, METHOD FOR
THE PREPARATION AND USE THEREOF
Abstract
Proposed is a polycondensation product comprising as monomer
components at least one aryl polyoxyalkylene ether, at least one
vicinally disubstituted aromatic compound, at least one aldehyde
and also optionally further aromatic compounds; processes for
preparing same, and also use thereof as dispersant for aqueous
suspensions of inorganic binders and as grinding assistant for
inorganic binders.
Inventors: |
Dierschke; Frank;
(Oppenheim, DE) ; Gadt; Torben; (Traunstein,
DE) ; Gehrig; Uwe; (St. Georgen, DE) ;
Melchart; Michael; (Ludwigshafen, DE) ; Vierle;
Mario; (Wasserburg, DE) ; Schwesig; Peter;
(Wasserburg, DE) ; Hartl; Klaus; (Tacherting,
DE) ; Stefan; Madalina Andreea; (Trostberg, DE)
; Mitkina; Tatiana; (Traunstein, DE) ; Pulkin;
Maxim; (Rosenheim, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Construction Research & Technology, GmbH |
Trostberg |
|
DE |
|
|
Family ID: |
48446247 |
Appl. No.: |
14/390703 |
Filed: |
April 3, 2013 |
PCT Filed: |
April 3, 2013 |
PCT NO: |
PCT/EP2013/056761 |
371 Date: |
October 3, 2014 |
Current U.S.
Class: |
524/3 ; 524/443;
528/148; 528/154 |
Current CPC
Class: |
C08G 12/40 20130101;
C04B 2103/52 20130101; Y02P 40/10 20151101; C04B 24/22 20130101;
C04B 24/302 20130101; C04B 24/30 20130101; C08G 16/0218 20130101;
C08G 8/28 20130101; C04B 2103/408 20130101; C04B 40/0039 20130101;
Y02P 40/20 20151101; C08G 16/0243 20130101; C04B 24/246 20130101;
C04B 40/0039 20130101; C04B 24/02 20130101; C04B 24/04 20130101;
C04B 24/10 20130101; C04B 24/122 20130101; C04B 24/123 20130101;
C04B 24/18 20130101; C04B 24/226 20130101; C04B 24/246 20130101;
C04B 24/2641 20130101; C04B 24/305 20130101; C04B 28/02
20130101 |
Class at
Publication: |
524/3 ; 528/148;
524/443; 528/154 |
International
Class: |
C04B 24/30 20060101
C04B024/30; C08G 16/02 20060101 C08G016/02 |
Foreign Application Data
Date |
Code |
Application Number |
Apr 11, 2012 |
EP |
12163706.0 |
Claims
1. A polycondensation product comprising as monomer components: A)
at least one aryl polyoxyalkylene ether of the formula (I)
##STR00004## where Ar is an aryl group, R.sub.1 and R.sub.2 each
independently of one another are selected from H, methyl and ethyl,
with optionally at least one of the groups R.sub.1 and R.sub.2
being H, m is an integer from 1 to 300 and R.sub.3 is selected from
the group consisting of H, alkyl, aryl, aralkyl, alkaryl,
phosphate, and also mixtures thereof; B) at least one aromatic
compound of the formula (II), ##STR00005## where R.sub.4 and
R.sub.5 each independently of one another are selected from H,
R.sub.8, OH, OR.sub.8, C(O)R.sub.8, COOH, COOR.sub.8, SO.sub.3H,
SO.sub.3R.sub.8 and NO.sub.2 and also alkali metal salts, alkaline
earth metal salts and ammonium salts thereof, or together are a
further fused-on ring, where R.sub.8 each independently is selected
from the group consisting of alkyl, aryl, aralkyl, alkaryl, and
R.sub.6 and R.sub.7 each independently of one another are selected
from OH, OR.sub.9, C(O)R.sub.9, COOH and COOR.sub.9 and also alkali
metal salts and alkaline earth metal salts and ammonium salts
thereof, where R.sub.9 each independently is selected from the
group consisting of alkyl, aryl, aralkyl, alkaryl; C) at least one
aldehyde; and also optionally D) at least one further aromatic
compound, selected from the group consisting of phenol,
2-phenoxyethanol, 2-phenoxyethyl phosphate and phosphonate,
2-phenoxyacetic acid, 2-(2-phenoxyethoxy)ethanol,
2-(2-phenoxyethoxy)ethyl phosphate and phosphonate,
2-[4-(2-hydroxyethoxy)phenoxy]ethyl phosphate and phosphonate,
2-[4-(2-phosphonatooxyethoxy)phenoxy]ethyl phosphate and
phosphonate, methoxyphenol, phenolsulphonic acid, furfuryl alcohol,
and also mixtures thereof.
2. The polycondensation product according to claim 1, characterized
in that the group Ar is an aryl group having 6 to 10 carbon atoms
in the ring system, optionally a phenyl group or a naphthyl
group.
3. The polycondensation product according to claim 1, characterized
in that m is an integer from 3 to 280, optionally from 10 to 160
and further optionally from 12 to 120.
4. The polycondensation product according to claim 1, characterized
in that R.sub.3 is selected from the group consisting of H,
C.sub.1-10 alkyl, C.sub.6-10 aryl, C.sub.7-11 aralkyl, C.sub.7-11
alkaryl and phosphate.
5. The polycondensation product according to claim 3, characterized
in that the oxyalkylene groups of the aryl polyoxyalkylene ether of
the formula (I) are selected from ethylene oxide groups and/or
propylene oxide groups, which are arranged randomly, alternatingly,
graduatedly and/or blockwise along the chain.
6. The polycondensation product according to claim 3, characterized
in that the aryl polyoxyalkylene ether of the formula (I) is a
polyethylene glycol monophenyl ether of the formula (III)
##STR00006## where m has the specified definition.
7. The polycondensation product according to claim 6, characterized
in that the polyethylene glycol monophenyl ether of the formula
(III) is a mixture with different values for m within the specified
definition.
8. The polycondensation product according to claim 1, characterized
in that R.sub.8 and R.sub.9 each independently are selected from H,
C.sub.1-10 alkyl, C.sub.6-10 aryl, C.sub.7-11 aralkyl and
C.sub.7-11 alkaryl.
9. The polycondensation product according to claim 1, characterized
in that the aromatic compound of the formula (II) is selected from
the group consisting of benzene-1,2-diol, benzene-1,2,3-triol,
2-hydroxybenzoic acid, 2,3- and 3,4-dihydroxybenzoic acid,
3,4,5-trihydroxybenzoic acid, phthalic acid, 3-hydroxyphthalic
acid, 2,3- and 3,4-dihydroxybenzenesulphonic acid, 1,2- and
2,3-dihydroxynaphthalene, 1,2- and 2,3-dihydroxynaphthalene-5- or
-6-sulphonic acid, and also mixtures thereof.
10. The polycondensation product according to claim 1,
characterized in that the aldehyde component C) is selected from
the group consisting of formaldehyde, paraformaldehyde, glyoxylic
acid, benzaldehyde, benzaldehydesulphonic acid,
benzaldehydedisulphonic acid, vanillin and isovanillin, and also
mixtures thereof.
11. The polycondensation product according to claim 1,
characterized in that the molar ratio of components C:(A+B) is from
1:3 to 3:1, optionally 1:2 to 2:1 and further optionally 1:0.9 to
1:1.1.
12. The polycondensation product according to claim 1,
characterized in that the molar ratio of components A:B is from
1:10 to 10:1, optionally 1:7 to 5:1 and further optionally 1:5 to
3:1.
13. The polycondensation product according to claim 1,
characterized in that the molar ratio of components D:(A+B) is from
0 to 3:1, optionally 0 to 2:1 and further optionally 0 to 1:1.
14. The polycondensation product according to claim 1 in the form
of a comb polymer with novolak structure.
15. The polycondensation product according to claim 1, having a
molecular weight in the range from 1000 to 100 000, optionally 2000
to 75 000 and further optionally 4000 to 50 000 g/mol.
16. A process for preparing the polycondensation product according
to claim 1, characterized in that components A), B), C) and
optionally D) are subjected to polycondensation in aqueous solution
at a temperature of 20 to 140.degree. C. under a pressure of 1 to
10 bar.
17. The process according to claim 16, characterized in that the
polycondensation takes place in the presence of an acidic catalyst
optionally selected from the group consisting of sulphuric acid,
methanesulphonic acid, p-toluenesulphonic acid, oxalic acid and
phosphoric acid, and also mixtures thereof.
18. The process according to claim 16, characterized in that after
conclusion of the polycondensation, the reaction mixture is
subjected to an aftertreatment at a pH of 8.0 to 13.0, at a
temperature of 60 to 120.degree. C. and optionally under a pressure
of 0.01 to 0.9 bar.
19. The process according to claim 18, characterized in that the pH
is adjusted by addition of an aqueous alkali, optionally NaOH, and
the salts formed during the neutralization are removed.
20. A process of utilizing the polycondensation product according
to claim 1 as a dispersant for aqueous suspensions of inorganic
binders selected from the group encompassing hydraulic binders,
latent hydraulic binders, pozzolanic binders, alkali-activated
and/or alkali-activatable aluminosilicate binders, and also
mixtures thereof.
21. The process according to claim 20, characterized in that: the
hydraulic binders are selected from cements, Portland cements and
aluminate cements, and also mixtures thereof, the latent hydraulic
binders are selected from industrial and/or synthetic slags, blast
furnace slag, slag sand, ground slag sand, electrothermic
phosphorus slag, stainless-steel slag, and also mixtures thereof,
and the pozzolanic binders are selected from amorphous silica,
precipitated silica, pyrogenic silica, microsilica, finely ground
glass, fly ash, brown-coal fly ash, mineral-coal fly ash,
metakaolin, natural pozzolans, tuff, trass and volcanic ash,
natural zeolites, and synthetic zeolites, and also mixtures
thereof.
22. The process according to claim 21, characterized in that the
alkali-activated aluminosilicate binders comprise the latent
hydraulic and/or the pozzolanic binders and also alkaline
activators, optionally aqueous solutions of alkali metal
carbonates, alkali metal fluorides, alkali metal hydroxides, alkali
metal aluminates, alkali metal silicates, soluble waterglass, and
also mixtures thereof.
23. The process according to claim 20 as a constituent of
construction material formulations and/or construction material
products on-site concrete, pre-cast concrete parts, concrete ware,
cast concrete stones in-situ concrete, air-placed concrete,
ready-mixed concrete, construction adhesives adhesives for thermal
insulation composite systems, concrete repair systems,
one-component sealing slurries, two-component sealing slurries,
screeds, filling and levelling compounds, tile adhesives, renders,
adhesives, sealants, coating systems optionally for tunnels,
wastewater channels, splash protection and condensate lines, dry
mortars, joint grouts, drainage mortars and/or repair mortars.
24. A process of utilizing the polycondensation product according
to claim 1 as a grinding assistant for inorganic binders selected
from the group encompassing hydraulic binders, latent hydraulic
binders and pozzolanic binders and/or alkali-activatable
aluminosilicate binders, and also mixtures thereof, wherein the
latent hydraulic binders are selected from industrial and/or
synthetic slags, blast furnace slag, slag sand, ground slag sand,
electrothermic phosphorus slag, stainless-steel slag, and also
mixtures thereof, and the pozzolanic binders are selected from
amorphous silica, precipitated silica, pyrogenic silica,
microsilica, finely ground glass, fly ash, brown-coal fly ash,
mineral-coal fly ash, metakaolin, natural pozzolans, tuff, trass,
volcanic ash, natural zeolites, and synthetic zeolites, and also
mixtures thereof.
25. The process according to claim 20 together with further
auxiliaries selected from the group encompassing glycols,
polyalcohols, amine alcohols, organic acids, amino acids, sugars,
molasses, organic salts, inorganic salts, polycarboxylate ethers,
naphthalenesulphonate, melamine/formaldehyde polycondensation
products, lignosulphonate, and also mixtures thereof.
Description
[0001] The present invention relates to a polycondensation product
comprising as monomer components at least one aryl polyoxyalkylene
ether, at least one vicinally disubstituted aromatic compound, at
least one aldehyde and also optionally further aromatic compounds;
to processes for preparing same, and also to the use thereof as
dispersants for aqueous suspensions of inorganic binders and as
grinding assistants for inorganic binders.
[0002] Portland cement was first referred to in British Patent BP
5022, since which time it has undergone continual further
development. It is nowadays considered one of the most widespread
inorganic binders. Portland cement hardens hydraulically by virtue
of its high CaO content.
[0003] Certain slags from metallurgical processes can be used in
the form of latent hydraulic binders as admixtures to Portland
cement. Also possible is activation with strong alkalis, such as
alkali metal hydroxides or waterglasses, for example.
[0004] Inorganic binder systems based on reactive, water-insoluble
compounds on the basis of SiO.sub.2 in conjunction with
Al.sub.2O.sub.3, which cure in an aqueous-alkali medium, are
likewise common knowledge. Cured binder systems of this kind are
also called "geopolymers" and are described for example in U.S.
Pat. No. 4,349,386, WO 85/03699 and U.S. Pat. No. 4,472,199.
[0005] Reactive oxide mixtures employed in this context include
metakaolin, microsilica, slags, fly ashes, activated clay,
pozzolans or mixtures thereof. The alkali medium for activating the
binders consists typically of aqueous solutions of alkali metal
carbonates, alkali metal fluorides, alkali metal hydroxides, alkali
metal aluminates and/or alkali metal silicates, such as soluble
waterglass. In comparison to Portland cement, geopolymers may be
more cost-effective and more stable, and may have a more favourable
CO.sub.2 emissions balance.
[0006] Aqueous cement suspensions are often admixed with admixtures
in the form of dispersants in order to improve their processing
properties, such as kneadability, fluidity, sprayability,
spreadability or pumpability. These admixtures are capable of
disrupting agglomerates, by adsorption to the surface of the
particles, and of dispersing the particles formed. Especially in
the case of highly concentrated dispersions, this results in a
marked improvement in processing properties.
[0007] In the production of cementitous construction material
mixtures such as concrete, this effect can be utilized to
particularly advantageous effect, since otherwise, in order to
achieve a readily processible consistency, substantially more water
would be needed than would be necessary for the subsequent
hydration process. As a result of this excess water, which
gradually evaporates after hardening has taken place, cavities
remain which significantly impair the mechanical strength and
robustness of the constructions. The said plasticizers or
dispersants are used in order to reduce the water fraction which is
excessive in the sense of hydration, and/or to optimize the
processing properties for a given water/cement ratio.
[0008] Examples of the cement dispersants or plasticizers used
primarily to date are salts of naphthalenesulphonic
acid/formaldehyde condensates (cf. EP 214412 A1; identified
hereinafter as naphthalenesulphonates), salts of melaminesulphonic
acid/formaldehyde condensates (cf. DE 1671017 A; identified below
as melaminesulphonates), and also salts of polycarboxylic acids
(cf. U.S. Pat. No. 5,707,445 B1, EP 1110981 A2, EP 1142847 A2;
identified below as polycarboxylates). Such polycarboxylates are
prepared mostly by radical copolymerization of ethylenically
unsaturated carboxylic acids (such as acrylic acid, methacrylic
acid or maleic acid and/or salts thereof) and poly(alkylene oxides)
having a polymerizable end group (such as methacrylates, allyl
ethers or vinyl ethers). This mode of preparation leads to polymers
having a comblike structure.
[0009] The activity of the molecules used derives from two
different effects. Firstly, the negatively charged acid groups of
the plasticizers adsorb on the cement grain surface, which is
positively charged through calcium ions. The electrostatic double
layer formed in this way results in electrostatic repulsion between
the particles, which is relatively weak, however. In the case of
the abovementioned comb polymers, this electrostatic repulsion is
reinforced additionally by the steric bulk of the non-adsorbing
poly(alkylene oxide) chains. This steric repulsion is very much
stronger than the electrostatic repulsion, and so it is easy to
explain why the plasticizing effect of the polycarboxylates is very
much greater than that of the naphthalene- or melamine-
sulphonates; in other words, in order to obtain comparable
plasticization, the polycarboxylate can be added at a significantly
lower rate.
[0010] WO 2006/042709 A1 describes a polycondensation product
consisting of A) an aromatic or heteroaromatic compound having 5 to
10 C atoms and/or heteroatoms, this compound possessing on average
1 to 300 oxyethylene and/or oxypropylene groups per molecule, which
are linked via an O or N atom to the aromatic or heteroaromatic
compound; and also, optionally, B) an aromatic compound selected
from the group of phenols, phenol ethers, naphthols, naphthol
ethers, anilines, furfuryl alcohols and/or an amino resin former
selected from the group of melamine (derivatives), urea
(derivatives) and carboxamides; and C) an aldehyde selected from
the group of formaldehyde, glyoxylic acid and benzaldehyde or
mixtures thereof, it being possible for the benzaldehyde to
contain, additionally, acid groups in the form of COOM.sub.a,
SO.sub.3M.sub.a and PO.sub.3M.sub.a, and for M to be H, alkali
metal or alkaline earth metal, ammonium or organic amine radicals,
and also for a to be 1/2, 1 or 2. It was found that this
polycondensation product produces very good plasticization in
hydraulic binders, such as cement. As compared with
naphthalenesulphonates or melaminesulphonates, it results in
substantially better plasticization of the construction material in
conjunction with a lower rate of addition, and the fluidity can be
maintained over a longer period of time. In WO 2006/042709 A1,
however, in contrast to the present invention, there is no
description as component B) of any vicinally disubstituted aromatic
compounds.
[0011] A further example of a polycondensation product is described
in EP 0780348 A1, as a dispersant for cement. In that patent,
components including alkoxylated phenol and hydroxybenzoic acids
are subjected to a polycondensation in the presence of
formaldehyde.
[0012] The aforementioned geopolymers exhibit distinct differences
relative to the cementitous systems, these differences making it
more difficult or impossible to use the stated plasticizers. In
order to obtain acceptable hardening times, the reactive oxide
components require strong alkaline activation. This higher level of
alkalinity imposes particular requirements on the dispersants,
these requirements, in the case of many commercial concrete
plasticizers, not being sufficiently ensured. Furthermore, these
low-calcium systems generally do not have any positively charged
grain surfaces. Instead, the surfaces are silicatic or SiO.sub.2
surfaces. Moreover, the high level of alkalinity that is required
for activation also constitutes a high salt load, which may annul a
dispersion effect that is possible at lower pH levels (comparably
to the cement).
[0013] The problem addressed by the inventors was that of
substantially avoiding at least some of the disadvantages of the
prior art discussed above. The intention more particularly was to
find dispersants which are capable of adsorbing to low-calcium
binders at relatively high pH levels and hence also of plasticizing
geopolymer systems. These dispersants ought to exhibit high
affinity for silicatic surfaces, preferably even at very high pH
levels. They ought ideally also to be suitable for the dispersing
of mixed systems comprising not only Portland cement but also
geopolymer raw materials, such as microsilica, slags, fly ashes,
clays, pozzolans or mixtures thereof (known as "supplemental
cementitious materials" or "SCM"); in other words, they ought also
to be suitable for composite cements in categories CEM II-V and
also CEM X (currently non-standardized composite cements with a
high level of SCM additions).
[0014] The problems identified above are solved with the features
of the independent claims. The dependent claims relate to preferred
embodiments.
[0015] It has surprisingly been found that the polycondensation
products of the invention, which comprise in the polymer chain at
least one vicinally disubstituted aromatic monomer component, such
as pyrocatechol, salicylic acid or dihydroxybenzoic acid, are
capable, even at relatively high pH levels, of dispersing
low-calcium inorganic binders, more particularly geopolymers. The
polyoxyalkylene groups attached by ether bonds, moreover, are
substantially more stable to hydrolysis than the polyoxyalkylene
groups, attached via ester bonds, of the known, prior-art
polycarboxylate ethers. Entirely surprisingly, the polycondensation
products of the invention are also suitable as grinding assistants
for inorganic binders.
[0016] The present invention accordingly provides a
polycondensation product comprising as monomer components: [0017]
A) at least one aryl polyoxyalkylene ether of the formula (I)
[0017] ##STR00001## [0018] where [0019] Ar is an aryl group, [0020]
R.sub.1 and R.sub.2 each independently of one another are selected
from H, methyl and ethyl, with preferably at least one of the
groups R.sub.1 and R.sub.2 being H, [0021] m is an integer from 1
to 300 and [0022] R.sub.3 is selected from the group consisting of
H, alkyl, aryl, aralkyl, alkaryl, phosphate, and also mixtures
thereof; [0023] B) at least one aromatic compound of the formula
(II),
[0023] ##STR00002## [0024] where R.sub.4 and R.sub.5 each
independently of one another are selected from H, R.sub.8, OH,
OR.sub.8, C(O)R.sub.8, COOH, COOR.sub.8, SO.sub.3H, SO.sub.3R.sub.8
and NO.sub.2 and also alkali metal salts, alkaline earth metal
salts and ammonium salts thereof, or together are a further
fused-on ring, where R.sub.8 each independently is selected from
the group consisting of alkyl, aryl, aralkyl, alkaryl, and R.sub.6
and R.sub.7 each independently of one another are selected from OH,
OR.sub.9, C(O)R.sub.9, COOH and COOR.sub.8 and also alkali metal
salts and alkaline earth metal salts and ammonium salts thereof,
where R.sub.9 each independently is selected from the group
consisting of alkyl, aryl, aralkyl, alkaryl; [0025] C) at least one
aldehyde; and also optionally [0026] D) at least one further
aromatic compound, selected from the group consisting of phenol,
2-phenoxyethanol, 2-phenoxyethyl phosphate and phosphonate,
2-phenoxyacetic acid, 2-(2-phenoxyethoxy)ethanol,
2-(2-phenoxyethoxy)ethyl phosphate and phosphonate,
2-[4-(2-hydroxyethoxy)phenoxy]ethyl phosphate and phosphonate,
2-[4-(2-phosphonatooxyethoxy)phenoxy]ethyl phosphate and
phosphonate, methoxyphenol, phenolsulphonic acid, furfuryl alcohol,
and also mixtures thereof.
[0027] Where at least one of the substituents in the general
formula (II) is a COOH group, it is preferred for the groups
R.sub.6 and R.sub.7 each to be OH groups.
[0028] The aryl group "Ar" is a homo- or heteroaryl group,
preferably a homoaryl group, having 6 to 10 carbon atoms in the
ring system, more particularly a phenyl group or a naphthyl group.
The group Ar may additionally be substituted by one or more further
groups, which are selected from C.sub.1-10 alkyl, C.sub.1-10
alkoxy, C.sub.6-10 aryl, C.sub.7-11 aralkyl, C.sub.7-11 alkaryl,
preferably methoxy.
[0029] The number "m" is preferably an integer from 3 to 280, more
preferably from 10 to 160 and more particularly from 12 to 120.
[0030] "R.sub.3" is preferably selected from the group consisting
of H, C.sub.1-10 alkyl, C.sub.6-10 aryl, C.sub.7-11 aralkyl,
C.sub.7-11 alkaryl and phosphate, with R.sub.3 being more
particularly H.
[0031] The oxyalkylene groups of the aryl polyoxyalkylene ether of
the formula (I) are preferably selected from ethylene oxide and/or
propylene oxide groups which are arranged randomly, alternatingly,
graduatedly and/or blockwise along the polyoxyalkylene chain.
[0032] With particular preference the aryl polyoxyalkylene ether of
the formula (I) is a polyethylene glycol monophenyl ether of the
formula (III),
##STR00003##
where m has the specified definition.
[0033] This polyethylene glycol monophenyl ether of the formula
(III) may also comprise a mixture having different values for m
within the definition specified above.
[0034] The abovementioned groups "R.sub.8" and "R.sub.9" are
preferably each independently of one another selected from
C.sub.1-10 alkyl, C.sub.6-10 aryl, C.sub.7-11 aralkyl and
C.sub.7-11 alkaryl and more particularly are H.
[0035] In accordance with particularly preferred embodiments, the
aromatic compounds of the formula (II) are selected from the group
consisting of benzene-1,2-diol, benzene-1,2,3-triol,
2-hydroxybenzoic acid, 2,3- and 3,4-dihydroxybenzoic acid,
3,4,5-trihydroxybenzoic acid, phthalic acid, 3-hydroxyphthalic
acid, 2,3- and 3,4-dihydroxybenzenesulphonic acid, 1,2- and
2,3-dihydroxynaphthalene, 1,2- and 2,3-dihydroxynaphthalene-5- or
-6-sulphonic acid, and also mixtures thereof.
[0036] More particularly preferred in this context are
benzene-1,2-diol, benzene-1,2,3-triol, 2,3- and
3,4-dihydroxybenzoic acid, 2,3- and 3,4-dihydroxybenzenesulphonic
acid, 1,2- and 2,3-dihydroxynaphthalene, 1,2- and
2,3-dihydroxynaphthalene-5- or -6-sulphonic acid, and also mixtures
thereof, while, for example, 2-hydroxybenzoic acid is less
preferred.
[0037] Here as well, as already stated generally in relation to
component B, alkali metal salts, alkaline earth metal salts and
ammonium salts of the corresponding acids are possible. For the
purposes of the present invention, "ammonium salts" is intended to
refer both to NH.sub.4.sup.+ salts and to salts of amines or
nitrogen-containing polymers such as, for instance,
polyethyleneimine salts. Moreover, as far as the completed
polycondensation product is concerned, it is immaterial whether the
said aromatic compounds are used directly as salts or whether these
salts are only obtained following an acidic polycondensation, by
neutralization. At very high pH levels, of the kind encountered in
the geopolymers sector, the amines and/or nitrogen-containing
polymers may also be present in free form.
[0038] The aldehyde component C) is preferably selected from the
group consisting of formaldehyde, paraformaldehyde, glyoxylic acid,
benzaldehyde, benzaldehydesulphonic acid, benzaldehydedisulphonic
acid, vanillin and isovanillin, and also mixtures thereof.
Formaldehyde as such or in the form of paraformaldehyde is
particularly preferred in this context.
[0039] The monomer components A, B, C and D (minus the water formed
in the polycondensation reaction) are present in particular molar
proportions in the polycondensation product of the invention. Thus
the molar ratio of component C:(A+B) is preferably 1:3 to 3:1, more
preferably 1:2 to 2:1 and more particularly 1:0.9 to 1:1.1.
[0040] The molar ratio of components A:B is preferably 1:10 to
10:1, more preferably 1:7 to 5:1 and more particularly 1:5 to 3:1.
The molar ratio of components D:(A+B) is preferably 0 to 3:1, more
preferably 0 to 2:1 and more particularly 0 to 1:1, with component
D representing an optional component.
[0041] The polycondensation product of the invention is preferably
in the form of a comb polymer with novolak structure. In other
words, in the case of formaldehyde as the aldehyde component, the
aromatic monomer components are joined to one another by means of
--CH.sub.2-- groups, since, as observed later on below, the
polycondensation reaction is carried out advantageously in the
acidic range. This produces molecular weights for the
polycondensation products that are situated preferably in the range
from 1000 to 100 000, more preferably in the range from 2000 to 75
000 and more particularly in the range from 4000 to 50 000
g/mol.
[0042] The present invention further provides a process for
preparing the polycondensation product of the invention, the said
process being characterized in that components A), B), C) and
optionally D) are subjected to polycondensation in aqueous solution
at a temperature of 20 to 140.degree. C. under a pressure of 1 to
10 bar.
[0043] If no sufficiently strong acid is used as monomer component
B, C or D, it is advisable to use an acidic catalyst. As acidic
catalyst it is possible to use an acid selected from the group
consisting of sulphuric acid, methanesulphonic acid,
p-toluenesulphonic acid, oxalic acid and phosphoric acid, and also
mixtures thereof.
[0044] Following the reaction according to the invention, the
reaction mixture may be subjected to an aftertreatment at a pH of
8.0 to 13.0, a temperature of 60 to 120.degree. C. and preferably a
pressure of 0.01 to 0.9 bar, more particularly in order to reduce
the amount of unreacted, free aldehyde component.
[0045] The said pH can be set by addition of an aqueous alkali,
such as NaOH, or a polyethyleneimine, and the salts formed during
the neutralization are advantageously removed.
[0046] The present invention additionally provides for the use of
the polycondensation products of the invention as dispersants for
aqueous suspensions of inorganic binders selected from the group
encompassing hydraulic binders, latent hydraulic binders,
pozzolanic binders, alkali-activated aluminosilicate binders, and
also mixtures thereof.
[0047] In this context, the said binders are advantageously
selected from the following groups:
the hydraulic binders from cements, more particularly from Portland
cement and aluminate cement, and also mixtures thereof, the latent
hydraulic binders from industrial and/or synthetic slags, more
particularly from blast furnace slag, slag sand, ground slag sand,
electrothermic phosphorus slag, stainless-steel slag, and also
mixtures thereof, and the pozzolanic binders from amorphous silica,
preferably precipitated silica, pyrogenic silica and microsilica,
finely ground glass, fly ash, preferably brown-coal fly ash and
mineral coal fly ash, metakaolin, natural pozzolans such as tuff,
trass and volcanic ash, natural and synthetic zeolites, and also
mixtures thereof.
[0048] Portland cement contains about 70% by weight CaO+MgO, about
20% by weight SiO.sub.2 and about 10% by weight
Al.sub.2O.sub.3+Fe.sub.2O.sub.3. Aluminate cement ("high-alumina
cement") contains about 20% to 40% by weight CaO, up to about 5% by
weight SiO.sub.2, about 40% to 80% by weight Al.sub.2O.sub.3 and up
to about 20% by weight Fe.sub.2O.sub.3. These cements are well
known in the art.
[0049] The slags may be both industrial slags, i.e. waste products
from industrial processes, and synthetically reproduced slags. The
latter is advantageous, since industrial slags are not always
available in consistent quantity and quality.
[0050] For the purposes of the present invention, a latent
hydraulic binder is preferably a binder in which the molar ratio of
(CaO+MgO):SiO.sub.2 is between 0.8 and 2.5 and more preferably
between 1.0 and 2.0.
[0051] Blast furnace slag, a typical latent hydraulic binder,
generally contains 30% to 45% by weight CaO, about 4% to 17% by
weight MgO, about 30% to 45% by weight SiO.sub.2 and about 5% to
15% by weight Al.sub.2O.sub.3, typically about 40% by weight CaO,
about 10% by weight MgO, about 35% by weight SiO.sub.2 and about
12% by weight Al.sub.2O.sub.3. The cured products generally have
the properties of hydraulically cured systems.
[0052] Blast furnace slag is a waste product of the blast furnace
process. Slag sand is granulated blast furnace slag, and ground
slag sand ("ground granulated blast furnace slag") is finely
pulverized slag sand. The ground slag sand varies, according to
origin and processing form, in its particle size and grain-size
distribution, with the particle size affecting the reactivity. As a
characteristic variable for the particle size, the figure known as
the Blaine value is employed, which is typically in the order of
magnitude of 200 to 1000, preferably between 300 and 500
m.sup.2kg.sup.-1. The finer the grind, the higher the
reactivity.
[0053] Electrothermic phosphorus slag is a waste product from the
production of phosphorus by electrothermic means. It is less
reactive than blast furnace slag and contains about 45% to 50% by
weight CaO, about 0.5% to 3% by weight MgO, about 38% to 43% by
weight SiO.sub.2, about 2% to 5% by weight Al.sub.2O.sub.3 and
about 0.2% to 3% by weight Fe.sub.2O.sub.3, and also fluoride and
phosphate. Stainless-steel slag is a waste product from various
steel manufacturing processes, with a highly varying composition
(see Caijun Shi, Pavel V. Krivenko, Della Roy, Alkali-Activated
Cements and Concretes, Taylor & Francis, London & New York,
2006, pp. 42-51).
[0054] Amorphous silica is preferably an X-ray-amorphous silica,
i.e. a silica which exhibits no crystallinity in a powder
diffraction procedure. The amorphous silica of the invention
advantageously has an SiO.sub.2 content of at least 80% by weight,
preferably at least 90% by weight. Precipitated silica is obtained
industrially via precipitation processes starting from waterglass.
Depending on the manufacturing method, precipitated silica is also
called silica gel. Pyrogenic silica is generated by reacting
chlorosilanes, such as silicon tetrachloride, in an oxyhydrogen
flame. Pyrogenic silica is an amorphous SiO.sub.2 powder with a
particle diameter of 5 to 50 nm and a specific surface area of 50
to 600 m.sup.2g.sup.-1.
[0055] Microsilica, also called silica dust, is a by-product of
silicon or ferrosilicon manufacture and likewise consists very
largely of amorphous SiO.sub.2 powder. The particles have diameters
in the order of magnitude of 0.1 .mu.m. The specific surface area
is in the order of magnitude of 15 to 30 m.sup.2g.sup.-1. In
contrast, commercial silica sand is crystalline and has
comparatively large particles and a comparatively low specific
surface area. In accordance with the invention it serves as an
inert aggregate.
[0056] Fly ashes are formed in operations including the combustion
of coal in power stations. Class C fly ash (brown coal fly ash)
contains, according to WO 08/012438 about 10% by weight CaO,
whereas class F fly ash (mineral coal fly ash) contains less than
8% by weight, preferably less than 4% by weight and typically about
2% by weight CaO.
[0057] Metakaolin is formed in the dehydrogenation of kaolin.
Whereas kaolin gives off physically bound water at 100 to
200.degree. C., dehydroxylation occurs at 500 to 800.degree. C.,
with collapse of the lattice structure and formation of metakaolin
(Al.sub.2Si.sub.2O.sub.7). Pure metakaolin, accordingly, contains
about 54% by weight SiO.sub.2 and about 46% by weight
Al.sub.2O.sub.3.
[0058] An overview of further pozzolanic binders suitable in
accordance with the invention is found for example in Caijun Shi,
Pavel V. Krivenko, Della Roy, Alkali-Activated Cements and
Concretes, Taylor & Francis, London & New York, 2006, pp.
51-63. Testing for pozzolan activity can take place in accordance
with DIN EN 196 Part 5.
[0059] According to one embodiment, therefore, the polycondensation
product of the invention is suitable as a dispersant for
alkali-activated aluminosilicate binders (geopolymers). According
to another embodiment, it is suitable for dispersing mixed systems
which comprise not only Portland cement but also geopolymer raw
materials, such as microsilica, slags, fly ashes, clays, pozzolans
or mixtures thereof (known as SCMs), i.e. for composite cements of
categories CEM II-V and also CEM X. (Use as a dispersant for pure
Portland cement or aluminate cement (CEM category I) is also
possible, although not especially interesting from an economic
standpoint.)
[0060] For the purposes of the present invention, "alkali-activated
alumosilicate binders" are binder systems which comprise latent
hydraulic and/or pozzolanic binders as defined above and also
alkaline activators, such as aqueous solutions of alkali metal
carbonates, alkali metal fluorides, alkali metal hydroxides, alkali
metal aluminates, alkali metal silicates (such as soluble
waterglass) and/or mixtures thereof. Conversely,
"alkali-activatable alumosilicate binders" mean binder systems of
the same kind which, although activatable by alkalis, have not yet
been activated. In both cases, the amount of Portland cement and/or
aluminate cement in total ought to be kept below 20% by weight,
preferably below 10% by weight, in order to rule out hydraulic
curing of the cement component. Furthermore, for the purposes of
the present invention, the dry alkaline activator or the solids
content of the aqueous alkaline activator is to be reckoned part of
the inorganic binder. Furthermore, mixtures of dry alkaline
activators and aqueous alkaline activators can also be used
advantageously.
[0061] The said alkali metal silicate is advantageously selected
from compounds having the empirical formula mSiO.sub.2.nM.sub.2O,
where M stands for Li, Na, K and NH.sub.4, and also mixtures
thereof, preferably for Na and K. The molar ratio m:n is
advantageously 0.5 to 4.0, preferably 0.6 to 3.0 and more
particularly 0.7 to 2.5. The alkali metal silicate is preferably
waterglass, more preferably a liquid waterglass, and more
particularly a sodium or potassium waterglass. Use may also be
made, however, of lithium or ammonium waterglasses, and also of
mixtures of the stated waterglasses.
[0062] The above-specified ratio m:n (also called "modulus") ought
preferably not to be exceeded, since otherwise it is no longer
likely that there will be any complete reaction of the components.
It is also possible to employ lower moduli, such as around 0.2.
Waterglasses having higher moduli ought before use to be adjusted
to moduli in the range according to the invention, using a suitable
aqueous alkali metal hydroxide.
[0063] Potassium waterglasses in the advantageous modulus range are
commercialized primarily as aqueous solutions, being highly
hygroscopic; sodium waterglasses in the advantageous modulus range
are also available commercially as solids. The solids contents of
the aqueous waterglass solutions are generally 20% by weight to 60%
by weight, preferably 30% to 50% by weight.
[0064] Waterglasses can be prepared industrially by melting silica
sand with the corresponding alkali metal carbonates. Alternatively
they may also be obtained without difficulty from mixtures of
reactive silicas with the corresponding aqueous alkali metal
hydroxides. In accordance with the invention, therefore, it is
possible to replace at least part of the alkali metal silicate by a
mixture of a reactive silica and the corresponding alkali metal
hydroxide.
[0065] The polycondensation product of the invention can be used as
a constituent of construction material formulations and/or
construction material products such as on-site concrete, pre-cast
concrete parts, concrete ware, cast concrete stones and also
in-situ concrete, air-placed concrete, ready-mixed concrete,
construction adhesives and adhesives for thermal insulation
composite systems, concrete repair systems, one-component and
two-component sealing slurries, screeds, filling and levelling
compounds, tile adhesives, renders, adhesives and sealants, coating
systems, more particularly for tunnels, wastewater channels, splash
protection and condensate lines, dry mortars, joint grouts,
drainage mortars and/or repair mortars.
[0066] In the case of cements in categories CEM I-V and also CEM X,
the dispersants ought advantageously to be added in the range from
0.01% to 2.0%, preferably from 0.05% to 2.0%, by weight, based on
the sum of the inorganic binders. (Not included in this reckoning
are, for example, fillers and aggregates, such as sands and
gravels, and also water and other possible additions).
[0067] Where the polycondensation product of the invention is used
as a dispersant for alkali-activated aluminosilicate binders
(geopolymers), nevertheless, the levels of addition ought to be
higher, on account of the sometimes low metering efficiency. The
level of addition of the dispersants here ought advantageously to
be in the range from 0.01% to 10.0%, preferably from 0.02% to 5.0%
and more particularly from 0.05% to 3.0%, by weight, based on the
sum of the inorganic binders.
[0068] The present invention additionally provides for the use of
the polycondensation products of the invention as grinding
assistants for inorganic binders, selected from the group
encompassing hydraulic binders, latent hydraulic binders and
pozzolanic binders as defined above, and/or alkali-activatable
aluminosilicate binders, and also mixtures thereof.
[0069] These grinding assistants facilitate the grinding of
cements, such as Portland cement and aluminate cement, i.e. of
cements of category CEM I, but also of composite cements of
categories CEM II-V and CEM X, of latent hydraulic binders and
pozzolanic binders, and also of alkali-activatable aluminosilicate
binders, which, as defined above, comprise dry alkaline
activators.
[0070] The level at which the grinding assistants are added here
ought advantageously to be in the range from 0.005% to 0.30%,
preferably from 0.01% to 0.05%, by weight, based on the sum of the
inorganic binders.
[0071] The grinding assistants and dispersants of the invention may
be used together with further additions or auxiliaries, selected
from the group encompassing glycols, polyalcohols, amine alcohols,
organic acids, amino acids, sugars, molasses, organic and inorganic
salts, polycarboxylate ethers, naphthalenesulphonate,
melamine-formaldehyde polycondensation products, lignosulphonate,
and also mixtures thereof. Further additives contemplated include
defoamers, water retention agents, pigments, fibres, dispersion
powders, wetting agents, retardants, accelerants, such as calcium
silicate hydrate, complexing agents, aqueous dispersions and
rheology modifiers.
[0072] Particularly noteworthy in this context is that when the
dispersants of the invention are used in combination with
commercial polycarboxylate ethers, the hydration of the composite
cement is significantly quicker in the case of approximately the
same metering efficiency.
[0073] The present invention is now elucidated with greater
precision by means of the examples below and the appended drawings.
In the drawing:
[0074] FIG. 1 shows a graphic representation of the particle size
distributions of ground slag sand as a function of the grinding
assistant used during cold grinding;
[0075] FIG. 2 shows a graphic representation of the particle size
distributions of ground slag sand as a function of the grinding
assistant used during hot grinding.
EXAMPLES
Example 1
[0076] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 320 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 49 parts of 3,4-dihydroxybenzoic acid and 16 parts of
paraformaldehyde. The reaction mixture is heated with stirring to
110.degree. C. until all of the solids have dissolved, and then 44
parts of methanesulphonic acid (70% strength--here and in all
subsequent syntheses, in the form of an aqueous solution) are added
over the course of 20 minutes at a rate such that the reaction
temperature does not exceed 115.degree. C. After the end of
metering, the reaction mixture is stirred at 110.degree. C. for a
further 3 hours. It is then left to cool, admixed with 350 parts of
water, heated to 100.degree. C. for 30 minutes and neutralized to a
pH of about 7.0 using 50% strength aqueous sodium hydroxide
solution.
Example 2
[0077] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 300 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 46 parts of vanillin (>99%,
4-hydroxy-3-methoxybenzaldehyde) and 14.9 parts of
paraformaldehyde. The reaction mixture is heated with stirring to
110.degree. C., and then 51.4 parts of methanesulphonic acid (70%)
are added over the course of 20 minutes at a rate such that the
reaction temperature does not exceed 115.degree. C. After the end
of metering, the reaction mixture is stirred at 110.degree. C. for
a further 2.5 hours. It is then left to cool, admixed with 350
parts of water, heated to 100.degree. C. for 30 minutes and
neutralized to a pH of about 7.0 using 50% strength aqueous sodium
hydroxide solution.
Example 3
[0078] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 400 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
5000 g/mol), 24.6 parts of 3,4-dihydroxybenzoic acid and 8 parts of
paraformaldehyde. The reaction mixture is heated with stirring to
115.degree. C., and then 38.4 parts of methanesulphonic acid (70%)
are added over the course of 10 minutes at a rate such that the
reaction temperature does not exceed 115.degree. C. After the end
of metering, the reaction mixture is stirred at 110.degree. C. for
a further 3 hours. It is then left to cool, admixed with 400 parts
of water, heated to 100.degree. C. for 30 minutes and neutralized
to a pH of about 7.0 using 50% strength aqueous sodium hydroxide
solution.
Example 4
[0079] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 80.degree. C. with 260 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 43 parts of pyrocatechol (1,2-dihydroxybenzene), 80
parts of water and 15.6 parts of paraformaldehyde. The reaction
mixture is subsequently admixed with 12.5 parts of methanesulphonic
acid (50%) over the course of 20 minutes at a rate such that the
reaction temperature does not exceed 80.degree. C. After the end of
metering, the reaction mixture is stirred at 80.degree. C. for a
further 2 hours. It is then left to cool, admixed with 350 parts of
water and neutralized to a pH of about 7.0 using 50% strength
aqueous sodium hydroxide solution.
Example 5
[0080] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 300 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 46.2 parts of 3,4-dihydroxybenzoic acid, 33 parts of
2-phenoxyethyl phosphate and 19.9 parts of paraformaldehyde. The
reaction mixture is heated with stirring to 110.degree. C., and
then 41 parts of methanesulphonic acid (70%) are added over the
course of 25 minutes at a rate such that the reaction temperature
does not exceed 115.degree. C. After the end of metering, the
reaction mixture is stirred at 110.degree. C. for a further 2.5
hours. It is then left to cool, admixed with 350 parts of water,
heated to 100.degree. C. for 30 minutes and neutralized to a pH of
about 7.0 using 50% strength aqueous sodium hydroxide solution.
[0081] The said 2-phenoxyethyl phosphate is synthesized generally
by charging a heatable reactor, equipped with stirrer and metering
pump, under nitrogen at 20.degree. C. with 621.8 parts of
2-phenoxyethanol. Subsequently, with cooling, 449.7 parts of
polyphosphoric acid are added over 100 minutes at a rate such that
the temperature does not rise above 35.degree. C. After the end of
metering, the reaction mixture is stirred at about 70.degree. C.
for a further 15 minutes and is discharged prior to
solidification.
Example 6
[0082] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 300 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 45.7 parts of vanillin (>99%,
4-hydroxy-3-methoxybenzaldehyde), 32.7 parts of 2-phenoxyethyl
phosphate and 19.9 parts of paraformaldehyde. The reaction mixture
is heated with stirring to 110.degree. C., and then 41.1 parts of
methanesulphonic acid (70%) are added over the course of 20 minutes
at a rate such that the reaction temperature does not exceed
115.degree. C. After the end of metering, the reaction mixture is
stirred at 110.degree. C. for a further 2.5 hours. It is then left
to cool, admixed with 350 parts of water, heated to 100.degree. C.
for 30 minutes and neutralized to a pH of about 7.0 using 50%
strength aqueous sodium hydroxide solution.
Example 7
[0083] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 300 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 45.6 parts of isovanillin
(3-hydroxy-4-methoxybenzaldehyde), 33 parts of 2-phenoxyethyl
phosphate and 19.9 parts of paraformaldehyde. The reaction mixture
is heated with stirring to 110.degree. C., and then 41 parts of
methanesulphonic acid (70%) are added over the course of 20 minutes
at a rate such that the reaction temperature does not exceed
115.degree. C. After the end of metering, the reaction mixture is
stirred at 110.degree. C. for a further 2 hours. It is then left to
cool, admixed with 350 parts of water, heated to 100.degree. C. for
30 minutes and neutralized to a pH of about 7.0 using 50% strength
aqueous sodium hydroxide solution.
Example 8
[0084] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 80.degree. C. with 300 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 72.1 parts of 2,3-dihydroxynaphthalene and 18.0 parts
of paraformaldehyde. The reaction mixture is subsequently admixed
with 12.5 parts of methanesulphonic acid (50%) over the course of
30 minutes at a rate such that the reaction temperature does not
exceed 80.degree. C. After the end of metering, the reaction
mixture is stirred at 80.degree. C. for a further 75 minutes. It is
then left to cool, admixed with 350 parts of water and neutralized
to a pH of about 7.0 using 50% strength aqueous sodium hydroxide
solution.
Example 9
[0085] A heatable reactor equipped with stirrer and metering pump
is charged with 225 parts of poly(ethylene oxide) monophenyl ether
(average molecular weight 750 g/mol) and 41.5 parts of
2-phenoxyethanol. Subsequently, with cooling, 66.0 parts of
polyphosphoric acid are added over 30 minutes and the mixture is
stirred at 90-95.degree. C. for 60 minutes. Added to this reaction
mixture at 90.degree. C. under a stream of nitrogen are 92.5 parts
of 3,4-dihydroxybenzoic acid and 39.8 parts of paraformaldehyde.
The reaction mixture is heated to about 100.degree. C. with
stirring, and then 57.6 parts of methanesulphonic acid (70%) are
added over the course of 25 minutes at a rate such that the
reaction temperature does not exceed 105.degree. C. After the end
of metering, the reaction mixture is stirred at 100.degree. C. for
a further 15 minutes. It is then left to cool, admixed with 350
parts of water and neutralized to a pH of about 7.0 using 50%
strength aqueous sodium hydroxide solution.
Example 10
[0086] A heatable reactor equipped with stirrer and metering pump
is charged with 225 parts of poly(ethylene oxide) monophenyl ether
(average molecular weight 750 g/mol) and 82.9 parts of
2-phenoxyethanol. Subsequently, with cooling, 99.0 parts of
polyphosphoric acid are added over 20 minutes and the mixture is
stirred at 90-95.degree. C. for 40 minutes. Added to this reaction
mixture at 90.degree. C. under a stream of nitrogen are 46.2 parts
of 3,4-dihydroxybenzoic acid and 39.8 parts of paraformaldehyde.
The reaction mixture is heated to about 100.degree. C. with
stirring and then 57.6 parts of methanesulphonic acid (70%) are
added over the course of 25 minutes at a rate such that the
reaction temperature does not exceed 105.degree. C. After the end
of metering, the reaction mixture is stirred at 100.degree. C. for
a further 15 minutes. It is then left to cool, admixed with 350
parts of water and neutralized to a pH of about 7.0 using
polyethyleneimine (Lupasol.RTM. G100, BASF SE).
Example 11
[0087] Aluminosilicate mortars were produced in accordance with the
following formula:
TABLE-US-00001 Microsilica 150 g Fly ash, type F 150 g Silica sand
700 g KOH (0.2%) 250 g
[0088] The starting materials were mixed in the laboratory with a
mortar mixer in accordance with DIN EN 196-1. The mixing operation
was carried out as described in DIN EN 196-1, with the difference
that the silica sand was added right at the beginning, and not only
subsequently, to the mixing trough. The alkaline activator used was
a 0.2% strength by weight aqueous KOH solution. All of the
polymeric dispersants were defoamed using Defoamer DF93 from BASF
SE or triisobutyl phosphate.
[0089] The dispersant was used as an aqueous solution as obtained
in the examples above. The level of addition in each case was 3 g
(calculated as solid). For comparison, determinations were made of
the slump without additive and with in each case 3 g of the
polycarboxylate ethers Melflux.RTM. 2453 (Comparative Example 1),
Glenium 51 (Comparative Example 2) and Melflux PCE 26L (Comparative
Example 3), all available from BASF SE.
[0090] The compositions of the ground slag sand and type F fly ash
were as follows [% by weight]:
TABLE-US-00002 remain- SiO.sub.2 Fe.sub.2O.sub.3 TiO.sub.2
Al.sub.2O.sub.3 CaO MgO K.sub.2O der Slag 34.0 0.4 1.1 11.6 43.0
7.3 0.5 2.1 sand Fly ash 53.4 5.7 1.1 26.8 3.1 2.0 4.5 3.4
[0091] The slump was determined in each case by tapping 15 times on
a slump table with a Hagermann cone (DIN EN 1015-3). The results
are shown in Table 1.
TABLE-US-00003 TABLE 1 Example Slump [cm] Density [g/cm.sup.3]
Without additive 19.9 1.94 Comparative Example 1 18.4 1.83
Comparative Example 2 18.9 1.95 Example 5 24.3 1.83 Example 6
>30.0 1.85 Example 7 >30.0 1.79
Example 12
[0092] Example 11 was repeated with the modification that 5.0%
strength by weight aqueous KOH solution was used as activator. The
results are shown in Table 2.
Formula:
TABLE-US-00004 [0093] Microsilica 150 g Fly ash, type F 150 g
Silica sand 700 g KOH (5.0%) 262.63 g
TABLE-US-00005 TABLE 2 Example Slump [cm] Density [g/cm3] Without
additive 17.5 1.96 Comparative Example 1 19.1 1.83 Comparative
Example 2 19.0 1.98 Example 1 28.4 1.96 Example 3 23.0 1.91 Example
5 >30.0 1.93
Example 13
[0094] Example 11 was repeated with the modification that ground
slag sand was used in the formulation. The results are shown in
Table 3.
Formula:
TABLE-US-00006 [0095] Ground slag sand 300 g Silica sand 700 g KOH
(0.2%) 250 g
TABLE-US-00007 TABLE 3 Example Slump [cm] Density [g/cm3] Without
additive 17.1 2.11 Comparative Example 1 22.7 2.00 Example 3 25.4
2.02 Example 5 25.8 2.03 Example 6 >30.0 2.05 Example 7 >30.0
2.13 Example 8 28.2 2.06
Example 14
[0096] Example 13 was repeated with the modification that 5.0%
strength by weight aqueous KOH solution was used as activator. The
results are shown in Table 4.
Formula:
TABLE-US-00008 [0097] Ground slag sand 300 g Silica sand 700 g KOH
(5.0%) 189.09 g
TABLE-US-00009 TABLE 4 Example Slump [cm] Density [g/cm3] Without
additive 17.4 2.12 Comparative Example 1 17.9 1.86 Comparative
Example 2 21.5 2.11 Example 1 28.4 2.09 Example 3 28.1 2.05 Example
5 >30.0 2.10 Example 6 >30.0 2.07 Example 7 >30.0 2.08
Example 15
[0098] Example 14 was repeated with the modification that a 3.3%
strength by weight aqueous Na.sub.2CO.sub.3 solution was used as
activator. The slump [in cm] was determined after 6 minutes and 30
minutes. The results are shown in Table 5.
Formula:
TABLE-US-00010 [0099] Ground slag sand 300 g Silica sand 700 g
Na.sub.2CO.sub.3 (3.3%) 181 g
TABLE-US-00011 TABLE 5 Slump Slump Density Example (6 min) (30 min)
[g/cm3] Without additive 17.5 16.6 2.00 Comparative Example 3 17.8
17.0 2.03 Example 9 20.4 19.9 2.01 Example 10 19.7 18.8 1.99
Example 16
[0100] Example 15 was repeated with the modification that a 3.3%
strength by weight aqueous Na.sub.2SiO.sub.3 solution was used as
activator. The slump [in cm] was determined after 6 minutes and 30
minutes. The results are shown in Table 6.
Formula:
TABLE-US-00012 [0101] Ground slag sand 300 g Silica sand 700 g
Na.sub.2SiO.sub.3 (3.3%) 181 g
TABLE-US-00013 TABLE 6 Slump Slump Density Example (6 min) (30 min)
[g/cm3] Without additive 17.6 16.1 1.99 Comparative Example 3 18.3
16.2 2.00 Example 9 20.0 19.0 1.97 Example 10 19.6 18.7 1.96
[0102] As becomes clear from these performance tests, the polymers
of the invention enable a distinct improvement in the consistency
of the aluminosilicate mortars in comparison to the sample without
dispersants. In some cases the flow of the mortar mixtures, as a
result of the addition of the polymers of the invention, exceeds
the dimensions of the 30 cm tapping board. A plasticizing
performance can be achieved here in different binding compositions
and with different activators such as KOH, Na.sub.2CO.sub.3 or
waterglass. Moreover, it can be seen that in contrast to the
polycarboxylate ethers, the plasticizing of alkali-activated
aluminosilicate binders is possible with the polymers of the
invention.
Example 17
[0103] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 320 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 44.2 parts of salicylic acid and 15.9 parts of
paraformaldehyde. The reaction mixture is heated with stirring to
110.degree. C. until all of the solids have dissolved, and then 66
parts of methanesulphonic acid (70%) are added over the course of
15 minutes at a rate such that the reaction temperature does not
exceed 110.degree. C. After the end of metering, the reaction
mixture is stirred at 110.degree. C. for a further 4 hours. It is
then left to cool, admixed with 350 parts of water, heated to
100.degree. C. for 30 minutes and neutralized to a pH of about 7.0
using 50% strength aqueous sodium hydroxide solution.
Example 18
[0104] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 320 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 44.2 parts of salicylic acid, 35 parts of
2-phenoxyethyl phosphate and 21.2 parts of paraformaldehyde. The
reaction mixture is heated with stirring to 110.degree. C. and then
44 parts of methanesulphonic acid (70%) are added over the course
of 15 minutes at a rate such that the reaction temperature does not
exceed 115.degree. C. After the end of metering, the reaction
mixture is stirred at 110.degree. C. for a further 2.75 hours. It
is then left to cool, admixed with 350 parts of water, heated to
100.degree. C. for 30 minutes and neutralized to a pH of about 7.0
using 50% strength aqueous sodium hydroxide solution.
Example 19
[0105] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 225 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight 750
g/mol), 82.9 parts of salicylic acid, 65.4 parts of 2-phenoxyethyl
phosphate, 25 parts of water and 39.8 parts of paraformaldehyde.
The reaction mixture is heated with stirring to 100.degree. C. and
then 115.2 parts of methanesulphonic acid (50%) are added over the
course of 40 minutes at a rate such that the reaction temperature
does not exceed 105.degree. C. After the end of metering, the
reaction mixture is stirred at 105.degree. C. for a further 4
hours. It is then left to cool, admixed with 400 parts of water and
neutralized to a pH of about 7.0 using 50% strength aqueous sodium
hydroxide solution.
Example 20
[0106] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 225 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight 750
g/mol), 165.7 parts of salicylic acid and 48.4 parts of
paraformaldehyde. The reaction mixture is heated with stirring to
95.degree. C. and then 57.6 parts of methanesulphonic acid (50%)
are added over the course of 25 minutes at a rate such that the
reaction temperature does not exceed 115.degree. C. After the end
of metering, the reaction mixture is stirred at 105.degree. C. for
a further 90 minutes. It is then left to cool, admixed with 300
parts of water and neutralized to a pH of about 7.0 using 50%
strength aqueous sodium hydroxide solution.
Example 21
[0107] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 225 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight 750
g/mol), 82.9 parts of salicylic acid, 65.4 parts of 2-phenoxyethyl
phosphate and 127.6 parts of formalin (30% strength in H.sub.2O).
The reaction mixture is heated with stirring to 100.degree. C. and
then 85.2 parts of sulphuric acid (70%) are added over the course
of 20 minutes at a rate such that the reaction temperature does not
exceed 105.degree. C. After the end of metering, the reaction
mixture is stirred at 105.degree. C. for a further 3 hours. It is
then left to cool, admixed with 300 parts of water, heated to
100.degree. C. for 30 minutes and neutralized to a pH of about 7.0
using 50% strength aqueous sodium hydroxide solution.
Example 22
[0108] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 90.degree. C. with 320 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight
2000 g/mol), 44.2 parts of salicylic acid, 22.1 parts of
2-phenoxyethanol and 21.2 parts of paraformaldehyde. Added to the
reaction mixture then are 43.9 parts of methanesulphonic acid (70%)
over the course of 15 minutes at a rate such that the reaction
temperature does not exceed 110.degree. C. After the end of
metering, the reaction mixture is stirred at 110.degree. C. for a
further 1 hour. It is then left to cool, admixed with 350 parts of
water, heated to 100.degree. C. for 30 minutes and neutralized to a
pH of about 7.0 using 50% strength aqueous sodium hydroxide
solution.
Example 23
[0109] A heatable reactor equipped with stirrer and metering pump
is charged under nitrogen at 95.degree. C. with 225 parts of
poly(ethylene oxide) monophenyl ether (average molecular weight 750
g/mol), 82.9 parts of salicylic acid, 65.4 parts of 2-phenoxyethyl
phosphate and 82.3 parts of methanesulphonic acid (70%). The
reaction mixture is heated with stirring to about 105.degree. C.
and then 128.2 parts of formalin (30% strength) are added over the
course of 70 minutes at a rate such that the reaction temperature
does not exceed 110.degree. C. After the end of metering, the
reaction mixture is stirred at 100.degree. C. for a further 4.75
hours. It is then left to cool, admixed with 300 parts of water and
neutralized to a pH of about 7.0 using 50% strength aqueous sodium
hydroxide solution.
Example 24
[0110] A heatable reactor equipped with stirrer and metering pump
is charged with 263 parts of poly(ethylene oxide) monophenyl ether
(average molecular weight 750 g/mol) and conditioned to 30.degree.
C. Then, over the course of 20 minutes, 42 parts of polyphosphoric
acid are added, followed by subsequent reaction for 15 minutes.
This reaction mixture is admixed with 96.7 parts of salicylic acid,
76.4 parts of 2-phenoxyethyl phosphate, 50 parts of water and 46.5
parts of paraformaldehyde under nitrogen at 95.degree. C. The
reaction mixture is heated to about 105.degree. C. with stirring,
and in this stage 66.2 parts of methanesulphonic acid (70%) are
added over the course of 30 minutes at a rate such that the
reaction temperature does not exceed 110.degree. C. After the end
of metering, the reaction mixture is stirred at 105.degree. C. for
a further 3.25 hours. It is then left to cool, admixed with 300
parts of water and neutralized to a pH of about 7.0 using 50%
strength aqueous sodium hydroxide solution.
Example 25
[0111] Example 12 was repeated with the salicylic acid-containing
polymers of Examples 19 to 24. The results are shown in Table
7.
Formulation:
TABLE-US-00014 [0112] Microsilica 150 g Fly ash, type F 150 g
Silica sand 700 g KOH (5.0%) 262.63 g
TABLE-US-00015 TABLE 7 Example Slump [cm] Density [g/cm3] Without
additive 17.5 1.95 Comparative Example 1 19.1 1.83 Comparative
Example 2 19.0 1.98 Example 19 23.5 1.95 Example 21 .gtoreq.30.0
1.92 Example 23 .gtoreq.30.0 1.91 Example 24 27.3 1.94
Example 26
[0113] Example 25 was repeated with the modification that 0.2%
strength by weight aqueous KOH solution was used as activator. The
results are shown in Table 8.
Formulation:
TABLE-US-00016 [0114] Microsilica 150 g Fly ash, type F 150 g
Silica sand 700 g KOH (0.2%) 250 g
TABLE-US-00017 TABLE 8 Example Slump [cm] Density [g/cm3] Without
additive 19.9 1.94 Comparative Example 1 18.4 1.83 Comparative
Example 2 18.9 1.95 Example 18 23.6 1.83 Example 19 25.4 1.85
Example 23 25.8 1.85 Example 24 .gtoreq.30.0 1.97
Example 27
[0115] Example 13 was repeated with the salicylic acid-containing
polymers of Examples 17 to 24. The results are shown in Table
9.
Formulation:
TABLE-US-00018 [0116] Ground slag sand 300 g Silica sand 700 g KOH
(0.2%) 180 g
TABLE-US-00019 TABLE 9 Example Slump [cm] Density [g/cm3] Without
additive 17.1 2.11 Comparative Example 1 22.7 2.00 Example 17 25.4
2.05 Example 18 .gtoreq.30.0 2.11 Example 19 29.3 2.05 Example 22
22.9 1.88 Example 23 28.5 2.01 Example 24 24.7 2.12
Example 28
[0117] Example 27 was repeated with the modification that 5.0%
strength by weight aqueous KOH solution was used as activator. The
results are shown in Table 10.
Formulation:
TABLE-US-00020 [0118] Ground slag sand 300 g Silica sand 700 g KOH
(5.0%) 189.09 g
TABLE-US-00021 TABLE 10 Example Slump [cm] Density [g/cm3] Without
additive 17.4 2.12 Comparative Example 1 17.9 1.86 Comparative
Example 2 21.5 2.11 Example 17 28.4 2.09 Example 18 .gtoreq.30.0
2.13 Example 19 .gtoreq.30.0 2.09 Example 21 .gtoreq.30.0 2.06
Example 22 .gtoreq.30.0 2.00 Example 23 .gtoreq.30.0 2.08 Example
24 29.3 2.07
Example 29
[0119] Example 28 was repeated with the modification that 15.0%
strength by weight aqueous KOH solution was used as activator. The
results are shown in Table 11.
Formulation:
TABLE-US-00022 [0120] Ground slag sand 300 g Silica sand 700 g KOH
(15%) 211.34 g
TABLE-US-00023 TABLE 11 Example Slump [cm] Density [g/cm3] Without
additive 18.6 2.07 Comparative Example 1 19.7 1.85 Comparative
Example 2 19.4 2.05 Example 19 23.7 2.11 Example 21 27.4 2.09
Example 24 .gtoreq.30.0 2.11
[0121] As these examples show, the polymers of the invention enable
a significant improvement in the consistency of the aluminosilicate
mortars. Here, the polymers of the invention permit an improvement
in the consistency of geopolymer systems with different binder
compositions, such as fly ashes, microsilica or ground slag sands,
and with different activator solutions. Moreover, it can be seen
from the tests that standard plasticizers such as polycarboxylic
ethers exhibit virtually no effect, whereas the polymers of the
invention enable outstanding plasticization and hence water
reduction.
Example 30
[0122] A heatable reactor equipped with stirrer and metering pump
is charged with 262.5 parts of poly(ethylene oxide) monophenyl
ether (average molecular weight 750 g/mol) and 48.4 parts of
2-phenoxyethanol. Subsequently, with cooling, 77.0 parts of
polyphosphoric acid are added over 15 minutes and the mixture is
stirred at about 95.degree. C. for 45 minutes. Added to this
reaction mixture at about 90.degree. C. under a stream of nitrogen
are 96.7 parts of salicylic acid, 50 parts of water and 46.5 parts
of paraformaldehyde. The reaction mixture is heated to about
90.degree. C. with stirring and then 67.3 parts of methanesulphonic
acid (70%) are added over the course of 30 minutes at a rate such
that the reaction temperature does not exceed 110.degree. C. After
the end of metering, the reaction mixture is stirred at about
100.degree. C. for a further 120 minutes. It is then left to cool,
admixed with 350 parts of water and neutralized to a pH of about
7.0 using aqueous sodium hydroxide solution (50%). The neutralized
dispersant is in the form of an about 35.0% strength by weight
aqueous solution.
Example 31
[0123] A heatable reactor equipped with stirrer and metering pump
is charged with 225 parts of poly(ethylene oxide) monophenyl ether
(average molecular weight 750 g/mol) and 82.9 parts of
2-phenoxyethanol. Subsequently, with cooling, 99.0 parts of
polyphosphoric acid are added over 35 minutes and the mixture is
stirred at about 90-95.degree. C. for 60 minutes. Added to this
reaction mixture under a stream of nitrogen are 41.4 parts of
salicylic acid, 40 parts of water and 39.8 parts of
paraformaldehyde. The reaction mixture is heated to about
85.degree. C. with stirring and then 57.7 parts of methanesulphonic
acid (70%) are added over the course of 35 minutes at a rate such
that the reaction temperature does not exceed 105.degree. C. After
the end of metering, the reaction mixture is stirred at 100.degree.
C. for a further 140 minutes. It is then left to cool, admixed with
350 parts of water and neutralized to a pH of about 7.0 using
polyethyleneimine (Lupasol.RTM. G100 from BASF SE). The neutralized
dispersant is in the form of an about 30.4% strength by weight
aqueous solution.
Example 32
[0124] Aluminosilicate mortars were produced in accordance with the
following formula:
TABLE-US-00024 Microsilica 150 g Fly ash, type F 150 g Silica sand
700 g Na.sub.2Al.sub.2O.sub.4 15 g Defoamer 0.12 g Water, total 250
g
[0125] The starting materials were mixed in the laboratory with a
mortar mixer in accordance with DIN EN 196-1. The mixing operation
was carried out as described in DIN EN 196-1, with the difference
that the silica sand was added right at the beginning, and not only
subsequently, to the mixing trough. The alkaline activator used was
the sodium aluminate dissolved in the make-up water. As the
defoamer, the product Defoamer DF40 from BASF SE was used. The
dispersant was used as an aqueous solution as obtained in Examples
1 and 2 (indicated as polymer solids content).
[0126] The compositions of the type F fly ash and the microsilica
were as follows [% by weight]:
TABLE-US-00025 SiO.sub.2 Fe.sub.2O.sub.3 TiO.sub.2 Al.sub.2O.sub.3
CaO MgO K.sub.2O Remainder Fly ash 53.4 5.7 1.1 26.8 3.1 2.0 4.5
3.4 Microsilica 98.1 0.0 0.0 0.0 0.23 0.2 0.77 0.7
[0127] The slump was determined after 6 minutes in each case by
tapping 15 times on a slump table with a Hagermann cone (DIN EN
1015-3). The results are shown in Table 12.
TABLE-US-00026 TABLE 12 Reference Example 30 Example 31 Dispersant
0.0 g 3.0 g 3.0 g Slump 18.6 cm 27.5 cm 27.3 cm
[0128] This table shows that the dispersants of the invention also
enable a significant improvement in the slumps of the
aluminosilicate mortar mixtures when in combination with sodium
aluminate as alkaline activator. Here, an improvement in
consistency is obtained both by Na salts and by polyethyleneimine
salts of the polymers of the invention.
Example 33
[0129] Example 3 was repeated. A fully water-soluble, brown polymer
was obtained which had a molecular weight (max. peak) Mp=24.3 kDa
(column combinations: OH-Pak SB-G, OH-Pak SB 804 HQ and OH-Pak SB
802.5 HQ from Shodex, Japan; eluent: 80% by volume aqueous ammonium
formate solution (0.05 mol/I) and 20% by volume acetonitrile;
injection volume 100 .mu.l; flow rate 0.5 ml/min).
Example 34
[0130] A heatable reactor equipped with stirrer, reflux condenser
and metering pump is charged with 150 parts of poly(ethylene oxide)
monophenyl ether (average molecular weight 750 g/mol), 101 parts of
hydroquinone bis(2-hydroxyethyl) ether and 28 parts of salicylic
acid and heated to 90.degree. C. under nitrogen. Then 132 parts of
polyphosphoric acid are added over the course of 33 minutes,
followed by subsequent reaction for 10 minutes. This reaction
mixture is admixed with 48 parts of methanesulphonic acid (70%) and
2 parts of water at 98.degree. C. The reaction mixture is cooled to
about 90.degree. C., with stirring, and 95 parts of formalin
solution (30%) are added over the course of 50 minutes at a rate
such that the reaction temperature does not exceed 110.degree. C.
After the end of metering, the reaction mixture is stirred at
100.degree. C. for a further 20 minutes. It is then left to cool,
admixed with 760 parts of water and neutralized to a pH of about
7.3 using 50% strength aqueous sodium hydroxide solution.
Example 35
[0131] A heatable reactor equipped with stirrer, reflux condenser
and metering pump is charged with 188 parts of poly(ethylene oxide)
monophenyl ether (average molecular weight 750 g/mol) and 35 parts
of phenoxyethanol and heated to 25.degree. C. under nitrogen. Then
55 parts of polyphosphoric acid are added over the course of 8
minutes, after which the reaction mixture is heated to 92.degree.
C. and subsequently reacted at this temperature for 100 minutes.
The reaction mixture is admixed with 104 parts of salicylic acid
and 69 parts of methanesulphonic acid (70%) and, after 10 minutes,
131 parts of formalin solution (30%) are added over the course of
60 minutes at a rate such that the reaction temperature does not
exceed 110.degree. C. After the end of metering, the reaction
mixture is stirred at 100.degree. C. for a further 3.5 hours. It is
then left to cool, admixed with 500 parts of water and neutralized
to a pH of about 7.3 using 50% strength aqueous sodium hydroxide
solution.
Example 36
[0132] A heatable reactor equipped with stirrer, reflux condenser
and metering pump is charged with 188 parts of poly(ethylene oxide)
monophenyl ether (average molecular weight 750 g/mol), and
additionally 28 parts of polyphosphoric acid are added under
nitrogen over the course of 8 minutes. After 10 minutes from the
end of metering, the reaction mixture is heated to 90.degree. C.
with stirring and subsequently reacted at around 95.degree. C. for
4 hours. Then 35 parts of phenoxyethanol and, 30 minutes later, 104
parts of salicylic acid and 69 parts of methanesulphonic acid (70%)
are added. The reaction mixture is heated to around 100.degree. C.
with stirring, and when that temperature has been attained, 132
parts of formalin solution (30%) are added over the course of 50
minutes at a rate such that the reaction temperature does not
exceed 110.degree. C. After the end of metering, the reaction
mixture is stirred at 95.degree. C. for a further 3.7 hours. It is
then left to cool, admixed with 450 parts of water and neutralized
to a pH of about 7.3 using 50% strength aqueous sodium hydroxide
solution.
Example 37
[0133] A heatable reactor equipped with stirrer, reflux condenser
and metering pump is charged with 135 parts of poly(ethylene oxide)
monophenyl ether (average molecular weight 750 g/mol), and
additionally 20 parts of polyphosphoric acid are added under
nitrogen over the course of 6 minutes. After 10 minutes from the
end of metering, the reaction mixture is heated to 90.degree. C.
with stirring and subsequently reacted at around 95.degree. C. for
4 hours. Then 50 parts of phenoxyethanol and, 15 minutes later, 149
parts of salicylic acid and 99 parts of methanesulphonic acid (70%)
are added. The reaction mixture is heated to around 90.degree. C.
with stirring, and when that temperature has been attained, 170
parts of formalin solution (30%) are added over the course of 60
minutes at a rate such that the reaction temperature does not
exceed 110.degree. C. After the end of metering, the reaction
mixture is stirred at 95.degree. C. for a further 2.75 hours. It is
then left to cool, admixed with 500 parts of water and neutralized
to a pH of about 7.3 using 50% strength aqueous sodium hydroxide
solution.
Example 38
[0134] Aluminosilicate mortars were produced in accordance with the
following formula:
TABLE-US-00027 Ground slag sand 300 g Silica sand 700 g KOH 12 g
Na.sub.2CO.sub.3 12 g Defoamer 0.12 g Water, total 175 g
[0135] The starting materials were mixed in the laboratory with a
mortar mixer in accordance with DIN EN 196-1. The mixing operation
was carried out as described in DIN EN 196-1, with the difference
that the silica sand was added right at the beginning, and not only
subsequently, to the mixing trough. The alkaline activator used was
the potassium hydroxide and sodium carbonate dissolved in the
make-up water. As the defoamer, the product Defoamer DF93 from BASF
SE was used. The dispersant was used as an aqueous solution as
obtained in Examples 1 and 2 (polymer solids content in the mortar
mixture: 3 g).
[0136] The composition of the ground slag sand was as follows [% by
weight]:
TABLE-US-00028 SiO.sub.2 Fe.sub.2O.sub.3 TiO.sub.2 Al.sub.2O.sub.3
CaO MgO K.sub.2O Remainder Slag 33.1 0.6 0.6 15.0 41.3 6.1 0.3 3.0
sand
[0137] The slump was determined after 6 minutes and after 30
minutes in each case by tapping 15 times on a slump table with a
Hagermann cone (DIN EN 1015-3). The results are shown in Table
13.
TABLE-US-00029 TABLE 13 Slump after Slump after Density Example 6
min [cm] 30 min [cm] [g/cm.sup.3] Without additives 15.7 15.2 1.98
Comparative example 16.6 15.5 1.96 (Melflux 2424) Example 34 16.6
16.3 2.05 Example 35 20.8 20.6 2.02 Example 36 23.7 23.3 2.08
Example 37 24.6 24.0 2.08
Example 39
[0138] Weighed out in a metal vessel were 100.0 g of a composite
slag sand cement of type CEM III/A 32.5 N. The amount of dispersant
indicated below, calculated as solids content, was mixed, taking
account in the calculation of the water present in the dispersant,
with the amount of water corresponding to a water/cement ratio of
0.3. In this context, the expression "bwoc" is intended to denote
"% by weight, based on the amount of cement". Following addition of
the water/dispersant mixture to the cement, the mixture was stirred
intensely with a paddle stirrer for 1 minute. The cement paste
obtained in this way was introduced into a metal cone (internal
diameter top/bottom 2.0/4.0 cm, height 6.0 cm) which stood on a
horizontally disposed glass plate. The metal cone was lifted, and
the cement paste underwent slump flow. The slump flow ("SF" or
"spread", diameter of the cement paste cake) was subsequently
determined at 3 points, and the average was taken. The averaged
values are shown in Table 14. (Glenium.RTM. SKY 115 is a commercial
high-performance dispersant from BASF Construction Polymers GmbH,
based on polycarboxylate ether.)
TABLE-US-00030 TABLE 14 Amount Amount added added SF Dispersant [g]
[bwoc] [cm] Comparative 1 Glenium .RTM. SKY 115 0.67 0.67% 10.8
Comparative 2 Glenium .RTM. SKY 115 0.34 0.34% <8 Example 39
Glenium .RTM. SKY 115 0.34 0.87% 10.6 Polycondensation 0.53
product
[0139] It was found that when the amount of high-performance
dispersant added was halved (Comparative 2), it was, as expected,
not possible to achieve the reference slump flow of the cement
paste from Comparative 1. Only by adding the polycondensation
product of the invention (Example 33) was it possible to bring back
the slump flow almost to the reference level.
[0140] A defined amount of the cement paste thus obtained was
transferred to a calorimeter, and the development of the heat of
hydration was recorded calorimetrically. For this purpose, the
calorimeter was equilibrated beforehand to 20.0.degree. C.
(isothermal reference calorimeter from TA Instruments, Model
TAM-AIR). After 48 hours, measurement was halted and the data was
evaluated. For this purpose, the differential heat generation dH/dt
(mW/g, standardized for 1 g of cement paste) and also the integral
heat generation H (J/g; after 6, 12, 24 and 48 hours) were
employed. The results are shown in Table 15.
TABLE-US-00031 TABLE 15 dH/dt max. H [J/g] [mW/g] at t [h, min] 6 h
12 h 24 h 48 h Comparative 1 1.58/23 h, 54 min 5.52 10.96 47.60
146.11 Example 39 1.66/18 h, 54 min 5.76 13.48 71.59 157.00
[0141] It was found that significantly quicker hydration was
achievable by using the polycondensation product from Example 33.
In spite of the addition of polymer at a higher level overall, a
significantly more rapid release of heat was observed, which
suggests a quicker hydration of the cement. The maximum in the heat
generation of the cement paste formulated using the
polycondensation product of the invention was achieved after just
18 hours and 54 minutes, whereas the cement paste formulated using
the commercial high-performance concrete plasticizer did not
achieve its maximum heat generation until 5 hours later. This is
also reflected in the integral heat generation; after 6, 12, 24 and
48 hours, the levels of heat generation observable were always
higher.
Example 40
[0142] Weighed out in a metal vessel were 100.0 g of a composite
slag sand/fly ash cement of type CEM V/A 32.5 N. The amount of
dispersant indicated below, calculated as solids content, was
mixed, taking account in the calculation of the water present in
the dispersant, with the amount of water corresponding to a
water/cement ratio of 0.33. Following addition of the
water/dispersant mixture to the cement, the mixture was stirred
intensely with a paddle stirrer for 1 minute. The cement paste
obtained in this way was introduced into a metal cone (internal
diameter top/bottom 2.0/4.0 cm, height 6.0 cm) which stood on a
horizontally disposed glass plate. The metal cone was lifted, and
the cement paste underwent slump flow. The slump flow was
subsequently determined at 3 points, and the average was taken. The
averaged values are shown in Table 16.
TABLE-US-00032 TABLE 16 Amount Amount added added SF Dispersant [g]
[bwoc] [cm] Comparative 3 Glenium .RTM. SKY 115 0.67 0.67% 17.0
Example 40 Glenium .RTM. SKY 115 0.34 0.67% 15.9 Polycondensation
0.33 product
[0143] It was found that when the amount of high-performance
dispersant was halved and the polycondensation product of the
invention was added, the reference slump flow of the cement paste
from Comparative 3 could be raised to close to the reference
level.
Example 41
[0144] Example 3 was repeated with 450 parts of poly(ethylene
oxide) monophenyl ether (average molecular weight 5000 g/mol), 27.3
parts of 3,4-dihydroxybenzoic acid, 9.3 parts of paraformaldehyde
and 49.4 parts of methanesulphonic acid (70%). The pH after
neutralization with 50% strength aqueous sodium hydroxide solution
was about 7.3. The polymer obtained was fully water-soluble and
dark brown, in the form of an about 32.4% strength by weight
aqueous solution. The molecular weight was about 12-23 kDa (Mp=11.6
and 22.5 kDa; GPC conditions as in Example 33).
Example 42
[0145] Example 20 was repeated with 262.5 parts of poly(ethylene
oxide) monophenyl ether (average molecular weight 750 g/mol), 145.0
parts of salicylic acid, 50 parts of water, 46.5 parts of
paraformaldehyde and 67.2 parts of methanesulphonic acid (70%). The
pH after neutralization with 50% strength aqueous sodium hydroxide
solution was about 7.3. The polymer obtained was fully
water-soluble and yellowish, in the form of an about 28.0% strength
by weight aqueous solution. The average molecular weight was about
5.4 kDa (GPC conditions as in Example 33).
Example 43
[0146] Example 20 was repeated with 300 parts of poly(ethylene
oxide) monophenyl ether (average molecular weight 2000 g/mol), 82.9
parts of salicylic acid, 26.1 parts of paraformaldehyde and 72.1
parts of methanesulphonic acid (50%). The reaction took place at
105-108.degree. C. The molecular weight was about 16 kDa.
Example 44
[0147] 12.3 kg of ground slag sand ("GBFS") from Salzgitter,
admixed with a 32.4% strength aqueous solution of the polymer from
Example 41 (identified as "E41" in FIG. 1 and in Tables 17 and 18)
or with a 28.0% strength aqueous solution of the polymer from
Example 42 (identified as "E42" in FIG. 1 and in Tables 17 and 18)
(in each case 0.03% by weight polymer, based on the weight of the
sand) were ground for 125 minutes with stainless steel balls in a
laboratory ball mill (LABBAS LM0504-S7, CEMTEC GmbH) without
additional external heating. The resulting powder was sieved
through a 5 mm sieve. For comparison, a GBFS sample without
addition of additives (identified as "blank" in FIG. 1) was ground
and sieved. The particle size distributions of the resultant
powders were determined using a Mastersizer 2000 from Malvern
Instruments, and the Blaine values were determined using a Blaine
analyser from SEGER Tonindustrie. The particle size distributions
are shown in FIG. 1. From each of the resulting samples of ground
slag sand, 700 g were separated into "coarse" and "fine" fractions,
using a 100 MZR (Plain) cyclone from Hosokawa Alpine with a set
limit particle size of 15 .mu.m, an air velocity of 49 m/s
(constant) and a rotational speed of 6000 rpm. For each of the
separated samples, the particle size distribution of the coarse and
fine fractions was measured.
Example 45
[0148] Example 44 was repeated. 0.08% by weight of each of the
following additives, based on the weight of the ground slag sand,
was used: "TEA" (triethanolamine), "RheoPlus 18" (44.2% strength
aqueous solution, containing 5% of the defoamer Plurafac LF305),
polymer from Example 41 (identified as "E41", in the form of a
32.4% strength aqueous solution, containing 5% of the defoamer
Plurafac LF305), polymer from Example 42 (identified as "E42", in
the form of a 28.0% strength aqueous solution, containing 5% of the
defoamer Plurafac LF305) and polymer from Example 43 (identified as
"E43" in FIG. 2, in the form of a 31.7% strength aqueous solution,
containing 5% of the defoamer Plurafac LF305). Grinding took place
at 120.degree. C. Here again, for comparison, a GBFS sample without
addition of additives (identified as "blank" in FIG. 2) was ground
and sieved. FIG. 2 shows the corresponding particle size
distributions.
DISCUSSION
[0149] FIG. 1 shows that the main difference in the particle size
distribution lies in the region of the coarse particles (15-300
.mu.m), in other words that the addition of the corresponding
grinding assistant leads to a reduction in the amount of coarse
particles, with a significant fall in the d (0.5) and d (0.9)
values with the grinding assistants, and a significant increase in
the Blaine values (cf. Table 17). The time for complete separation
of the fractions is shortened when the grinding assistants of the
invention are used, with beneficial consequences for the energy
costs, and the average particle size of the coarse fraction is
significantly reduced (cf. Table 18). From this it can be inferred
that the polycondensation products of the invention enhance the
grindability of the slag.
TABLE-US-00033 TABLE 17 Sample d (0.1) d (0.5) d (0.9) d (0.450) d
(0.632) n Blaine Density GBFS "E42" 1.403 10.556 45.621 8.816
16.885 1.03 3937 2.891 GBFS "E41" 1.375 10.69 49.021 8.875 17.391
0.98 3902 2.897 GBFS "blank" 1.419 11.528 65.982 9.38 20.158 0.97
3758 2.905
TABLE-US-00034 TABLE 18 d (0.5) of the d (0.5) of the coarse/fine
separation time fine fraction coarse fraction Sample (m/m) [min]
[.mu.m] [.mu.m] "E42" 1.15 31 5.645 29.553 "E41" 0.76 31 5.584
28.249 "blank" 0.71 38 5.413 36.618
[0150] FIG. 2 and Table 19 show particle size distributions and
Blaine values of slag sands ground hot with the various additives
identified in Example 40. The average particle sizes d (0.5) of the
slag sands ground with the polymers "E42" and "E43" are
significantly smaller, and the corresponding Blaine values higher,
than those of the sample without additives ("blank") and of the
sample ground with "TEA" or RheoPlus 18 (high-performance cement
plasticizer from BASF SE).
TABLE-US-00035 TABLE 19 Sample d (0.5) d (0.9) Blaine value GBFS +
"E42" 10.54 43.36 3818 GBFS + "E43" 10.72 44.01 3877 GBFS + "TEA"
11.12 41.25 3735 GBFS + "RheoPlus 18" 11.72 45.17 3560 GBFS + "E41"
11.86 48.08 3612 GBFS "blank" 12.23 72.43 3482
* * * * *